Bisguanamine

ABSTRACT

There are described new bisguanamines of the formula ##STR1## where n is a number from 10 to 20 and their production. The bisguanamines are stabilizers for formaldehyde solutions and have outstanding qualifications and action for this purpose.

This is a division, of application Ser. No. 146,247 filed May 5, 1980,now U.S. Pat. No. 4,339,578.

BACKGROUND OF THE INVENTION

The invention is directed to new bisguanamines and their use in thestabilization of formaldehyde solutions.

There are already known phenylene bisguanamines of the formula ##STR2##(see German AS No. 2,358,856). Besides there are known alkylenebisguanamines of the formula ##STR3## in which n is a number from 1 to8, see Booth, Chemistry and Industry August 3, 1968, page 1047. Theentire disclosure of Booth is hereby incorporated by reference andrelied upon.

Aqueous formaldehyde solutions, especially solutions having aformaldehyde content above 30 weight percent are unstable if thetemperatures at which they are stored fall below a certain minimum.There occurs turbidity through the formation of formaldehyde oligomersand finally the precipitation of paraformaldehyde. The higher theconcentration of formaldehyde and the lower the storage temperature themore unstable are the solutions. Accordingly to the data in themonograph, "Formaldehyde" by J. F. Walker, 3rd edition, page 95, a 30percent formaldehyde solution remains stable for up to about 3 months ifit is held at at least 7° C. For a 37 percent solution the requiredminimum temperature is 35° C., for a 45% solution 55° C. and for a 50%solution 65° C. However, a disadvantage of the use of higher storagetemperatures is that formic acid forms to a considerable extent in theformaldehyde solutions. This causes corrosion and is particularlydisturbing in the use of formaldehyde solutions for condensationreactions.

The above mentioned values refer to formaldehyde solutions which containless than 1 weight percent methanol as a stabilizer. To be sure by usinghigher methanol concentrations there can be produced equal storabilityat lower temperature, but there are required disproportionately highmethanol concentrations. For example there is needed in a 37 percentformaldehyde solution for a storage temperature of 21° C., a methanolcontent of 7%, for 7° C. a methanol content of 10% and for 6° C. amethanol content of 12%. The addition of methanol, however considerablyincreases the cost of the formaldehyde solutions, especially since themethanol is generally lost in using the solutions. Apart therefromthrough the methanol the speed of reaction in numerous condensationreactions, for example in the condensation with melamine, is reduced.

Besides methanol there are known as stabilizers (for formaldehyde),ethanol, propanol-1, propanol-2, ethylene glycol, glycerine, urea,methyl urea, dimethyl urea, thiourea, diethyl thiourea, formamide,melamine, methylol melamine and acetoxime (J. F. Walker, Formaldehyde",third edition, page 95, U.S. Pat. No. 2,000,152 , U.S. Pat. 2,002,243and Swain U.S. Pat. No. 2,237,092). However, these materials must beused in concentrations of at least 2% to be effective.

Stabilizing agents which can be used in lower concentrations are forexample ether, acetals of polyhydric alcohols such as pentaerythritol,sorbitol and polyethylene glycol, esters of these polyhydric alcoholsand higher fatty acids, higher alcohols such as heptanol, octanol,decanol, hydroquinone, polyvinyl alcohol, its esters and acetals(Halpern U.S. Pat. No. 3,183,271; British patent 1,129,507 Japanese Pat.No. 30-3396. However, a disadvantage is that the activity of thesematerials is insufficient at lower concentrations and temperatures.

Furthermore, it is known to add as stabilizers lipophilic colloids suchas polyoxyethylene lauryl ether (HLB (hydrophilic, lipophilicbalance)-value=9.5), lipophilic sorbital esters of higher fatty acidssuch as sorbitol monolaurate (HLB value=8.6) or soluble or partiallysoluble hydrophilic colloids such as methyl cellulose, hydroxypropylmethyl cellulose, ethyl cellulose, gelatin, pectin and celluloseacetostearate. They are used in concentrations below 0.1% or below 0.5%(German OS 1443566, Prinz U.S. Pat. No. 3,137,736). Also in these casesthe stabilizing action in formaldehyde solutions having a methanolcontent below 1% at low temperatures is not sufficient.

There also have been used as stabilizers 2,4-diaminotriazine (1,3,5) orits methylol derivatives which contain in the 6-position an aliphaticresidue having 7 to 9 carbon atoms or an alkoxy or an alkylmercaptogroup having 5 to 10 carbon atoms (Bornmann German Pat. No. 1205073 andBelgian Pat. No. 719245). Bornmann shows that alkyl guanamines having analkyl chain length of below 7 carbon atoms or above 9 carbon atoms arepoorer stabilizers than those with 7 to 9 carbon atoms. The stabilizereffect goes down even further as the alkyl group increases from 11 to 15carbon atoms. For a good stabilizing effect the concentration of theadded aminotriazine must be 0.05 to 0.2%.

There have also been employed for stabilizing formaldehyde solutions,mixtures of guanamines, for example butyroguanamine, benzoguanamine,acetoguanamine and their methylol derivatices with fatty acid esters,ethers or acetals of a polyhydric alcohol, hydroquinone, polyvinylalcohol as well as esters or acetals of polyvinyl alcohol. In thesemixtures the guanamine must be used in concentrations of 0.08%,especially of 0.1% if a sufficient activity is to be attained (Matsuora,German AS 1219464).

Besides it is known to use as stabilizers methoxymethyl, ethoxymethyl,propoxymethyl and butoxymethyl derivatives of aceto-, propio-, butyro-and benzoguanamines which are mixed with reaction products offormaldehyde with ethylene glycol, propylene glycol, polyethyleneglycol, polypropylene glycol, glycerine, trimethylolpropane,pentaerythritol, sorbitol or polyvinyl alcohol and with aceto-, propio-,butryo- or benzoguanamine or with methyl-, ethyl-, propyl-, butyl-,cyclohexyl-, benzyl- or phenyl melamine (Ishizuka German AS 12268608).The concentrations in which the various guanamines or their mixtures areemployed lie between 0.0025 and 0.06%. However, at these low stabilizersconcentrations an elevated storage temperature is required if there isto be produced a sufficient stability of the formaldehyde solutions. Ifhigher concentrations, namely 0.001 to 0.1% of the guanamine are usedwith 0.1 to 1.0% of melamine (Dakli German Pat. No. 1768915) it is truethat the stabilization is better but the reactibility of theformaldehyde for condensation is reduced considerably.

It is also known that the activity of the guanamines or their methylolderivatives can be increased if there are additionally used hydrophilicpolyglycol ethers of fatty alcohols or of partial esters of polyhydricalchols with fatty acids or ion-active surface active substances such asphosphoric acid esters of nonylphenyl polyethylene glycols. However,also in these cases the activity is still not satisfactory.

Finally there is also known the employing of phenylene bisguanamine asstabilizer (Diem, German As No. 2358856). This material it is true showsa better activity, however, it is relatively difficulty accessible andparticularly exhibits the disadvantage that it is very difficultlysoluble. Therefore it is difficult and requires much time to bring thenecessary amount of stabilizer into soluble form. The alkylenebisguanamines (II) are to be sure considerably easier to dissolve, butthey have either no stabilizing effect or only very small stabilizingeffect.

SUMMARY OF THE INVENTION

There have now been found alkylene bisguanamines of the formula ##STR4##where n is a number from 10 to 20. Thus n can be 10, 11, 12, 14, 16, 18or 20 for example.

The alkylene bisguanamines of the invention can be produced in the sameway as the known alkylene bisguanamines (II), for example by reaction ofthe corresponding aliphatic dinitrile with dicyandiamide in a polarsolvent such as dimethyl sulfoxide, corresponding to the process inBooth, Chemistry and Industry 1968, page 1047.

For example for the production of dodecanobisguanamine there is employed1,10-dicyanodecane, for the production of hexadecanobisguanamine thereis employed 1,14-dicyanotetradecane, for the production ofoctadecanobisguanamine there is employed 1,16-dicyanohexadecane, for theproduction of eicosanobisguanamine there is employed1,18-dicyanooctadecane and for the production of decanobisguanaminethere is employed 1,8-dicyanooctane.

Furthermore there has now been found a process for the stabilization offormaldehyde solutions, those having a methanol content of less than 1%being preferred, using bisguanamines as stabilizers wherein there areemployed as stabilizers the alkylene bisguanamines (III) of theinvention. While the known alkylene bisguanamines (II) are unsuited forthis purpose, the compounds (III) of the invention act produceoutstanding stabilization. In contrast to phenylene bisguanamine (I)they have the particular advantage that they are considerably morereadily soluble and therefore much easier to use.

According to the invention there are preferably employed as stabilizersthe alkylene bisguanamines of formula III in which n is a number from 10to 16, especially a number from 14 to 16.

The amount of the stabilizer to add to the formaldehyde solution dependsin a given case to a certain degree on the formaldehyde content and thestorage temperature of the solutions. In most cases there is employed astabilizer content between 0.001 and 0.5 weight percent. Preferablythere are chosen stabilizer contents between 0.005 and 0.10,particularly between 0.01 and 0.03 weight percent.

Unless otherwise indicated all parts and percentages are by weight.

The process can comprise, consist essentially of or consists of thesteps set forth and the compositions can comprise, consist essentiallyof or consist of the materials set forth.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(a) Production of the Alkylene Bisguanamine

EXAMPLE 1

There were dissolved in 500 ml of dimethyl sulfoxide 210 grams (2.5moles) of dicyandiamide, which hereby was warmed to 60° C. There wereintroduced into this solution 192 grams (1.0 mole) of 1,10-dicyanodecaneand then there were added 30 grams of a 50% aqueous potassium hydroxidesolution. The mixture was heated to 135° C., held at this temperaturefor 45 minutes, then cooled to 100° C. and finally diluted to double itsvolume through the addition of 500 ml of water. There was separated fromthe warm mixture the precipitated dodecano-bisguanamine. It was washedwith water and recrystallized from dimethyl sulfoxide. The yield was 346grams, corresponding to 96% based on the 1,10-dicanodecane employed. Thedodecanobisguanamine had a melting point of 290° C. The elementedanalysis was

    ______________________________________                                                  C           H     N                                                 ______________________________________                                        found       53.0          8.0   38.7                                          calculates as                                                                 C.sub.16 H.sub.28 N.sub.10                                                                53.3          7.8   38.9                                          ______________________________________                                    

The dodecanobisguanamine was identified by IR and NMR spectroscopicallyand also mass spectrographically.

EXAMPLE 2

The procesure was the same as in Example 1 but there was reacted1,11-dicyanoundecane to form tridecanobisguanamine. Melting point of theguanamine: 219° C. Elemental analysis:

    ______________________________________                                                  C           H     N                                                 ______________________________________                                        found       55.0          7.6   37.3                                          calculated as                                                                 C.sub.17 H.sub.30 N.sub.10                                                                54.5          8.0   37.5                                          ______________________________________                                    

EXAMPLE 3

The procedure was the same as in Example 1 but there was reacted1,12-dicanododecane to form tetradecanobisguanamine. Melting point ofthe guanamine: 180° C. Elemental analysis:

    ______________________________________                                                  C           H     N                                                 ______________________________________                                        found       56.7          8.5   34.5                                          calculated as                                                                 C.sub.18 H.sub.32 N.sub.10                                                                56.8          8.5   35.7                                          ______________________________________                                    

EXAMPLE 4

The procedure was the same as in Example 1 but there was reacted1,4-dicyanotetradecane to form hexadecanobisquanamine. Melting point ofthe guanamine: 219° C.

Elemental analysis:

    ______________________________________                                                  C           H     N                                                 ______________________________________                                        found       58.5          8.5   32.8                                          calculated as                                                                 C.sub.20 H.sub.36 N.sub.10                                                                57.7          8.7   33.6                                          ______________________________________                                    

EXAMPLE 5

The procedure was the same as in Example 1 but there was reacted1,16-dicyanohexadecane to form octadecanobisguanamine. Melting point ofthe quanamine: 230° C. Elemental analysis:

    ______________________________________                                                  C           H     N                                                 ______________________________________                                        found       59.2          9.1   31.7                                          calculated as                                                                 C.sub.22 H.sub.40 N.sub.10                                                                59.4          9.1   31.5                                          ______________________________________                                    

(B) Stabilization of the Formaldehyde Solutions

There were used formaldehyde solutions with differing contents offormaldehyde and methanol. To these solutions there were added differentamounts of bisguanamines as stabilizers and there was examined how longthese solutions were stable at a specific storage temperature.

To dissolve the stabilizers in the formaldehyde solutions these wereheld in each case at 50° C. with stirring for 20 to 30 minutes.

The results are collected in the following tables. The stabilizers, thebisguanamines, are designated by n, the number of methylene groupsaccording to formula III. The stabilizer contents are given in weightpercents based on the total formaldehyde solution. As storability therewas considered the time in which the solution was stable. The solutionswere regarded as stable until there occurred the first separation justdetectable by the eye.

                  TABLE 1                                                         ______________________________________                                        Solutions containing 37 weight percent formaldehyde                           and 0.30 weight percent methanol; pH 4.2.                                     Stabilizer         Storage   Storability                                      Nr.    Type n  Content %   Temp. °C.                                                                      Days                                       ______________________________________                                        1      10      0.020       0       20                                         2      10      0.030       0       >120                                       3      11      0.020       0       30                                         4      12      0.020       0       >90                                        5      12      0.030       0       >120                                       6      14      0.010       0       >120                                       7      16      0.005       0       10                                         8      16      0.010       0       >120                                       ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Solutions containing 40 weight percent formaldehyde                           and 0.40 weight percent methanol; pH 4.1                                      Stabilizer         Storage   Storability                                      Nr     Type n  Content %   Temp. °C.                                                                      Days                                       ______________________________________                                         9     10      0.020       10      70                                         10     10      0.030       10      >120                                       11     11      0.020       10      >120                                       12     12      0.020       10      >120                                       13     12      0.010       0       5                                          14     14      0.010       10      >120                                       15     16      0.010       0       7                                          16     16      0.010       10      >120                                       ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Solutions containing 44 weight percent formaldehyde                           and 0.45 weight percent methanol; pH 3.9.                                     Stabilizer         Storage   Storability                                      Nr     Type n  Content %   Temp. °C.                                                                      Days                                       ______________________________________                                        17     10      0.010       25      2                                          18     10      0.015       25      >60                                        19     11      0.015       25      >60                                        20     12      0.010       25      19                                         21     12      0.015       25      >60                                        22     14      0.010       25      >60                                        22     16      0.010       25      >60                                        ______________________________________                                    

The entire disclosure of German Priorty application No. P 2919496.5 ishereby incorporated by reference.

What is claimed is:
 1. An aqueous formaldehyde solution containing astabilizing effective amount of an alkylene bisguanamine of the formula##STR5## where n is an integer of 10 to
 20. 2. An aqueous formaldehydesolution according to claim 1 wherein n is 10 to
 16. 3. An aqueousformaldehyde solution according to claim 2 wherein n is 14 to
 16. 4. Anaqueous formaldehyde solution according to claim 1 containing methanol.5. An aqueous formaldehyde solution according to claim 4 wherein themethanol content is less than 1 weight percent.
 6. An aqueousformaldehyde solution according to claim 5 wherein the methanol contentis 0.30 to 0.45 weight percent.
 7. An aqueous formaldehyde solutionaccording to claim 6 wherein the methanol content is 0.30 weightpercent.
 8. An aqueous formaldehyde solution according to claim 1wherein the alkylene bisguanamine is employed in an amount of 0.001 to0.5 weight percent.
 9. An aqueous formaldehyde solution according toclaim 8 containing methanol, the amount of methanol being less than 1weight percent.
 10. An aqueous formaldehyde solution according to claim9 wherein the amount of methanol is at least 0.30 weight percent.
 11. Anaqueous formaldehyde solution according to claim 9 wherein n is 14 to16.
 12. An aqueous formaldehyde solution according to claim 8 whereinthe alkylene bisguanamine is employed in an amount of 0.005 to 0.1weight percent.
 13. An aqueous formaldehyde solution according to claim12 containing methanol, the amount of methanol being less than 1 weightpercent.
 14. An aqueous formaldehyde solution according to claim 12wherein the alkylene bisguanamine is employed in an amount of 0.01 to0.3 weight percent.
 15. An aqueous formaldehyde solution according toclaim 14 containing methanol, the amount of methanol being less than 1weight percent.
 16. An aqueous formaldehyde solution according to claim15 wherein n is 14 to
 16. 17. An aqueous formaldehyde solution accordingto claim 15 wherein the amount of bisguanamine is 0.01 weight percent.18. An aqueous formaldehyde solution according to claim 8 containing 30to 50 weight percent formaldehyde.
 19. An aqueous formaldehyde solutionaccording to claim 18 containing methanol, the amount of methanol beingless than 1 weight percent.